CN102800809B - Use the organic electronic device of the simplification of the polymeric anode with high work function - Google Patents

Abstract

The present invention relates to simplified organic electronic devices using polymer anodes with high work function.

Description

Simplified organic electronic devices using polymer anodes with high work function

Cross references to related patent applications

This application claims the benefit of Korean Patent Application No. 10-2011-0050845 filed with the Korean Intellectual Property Office on May 27, 2011, the disclosure of which is incorporated herein by reference in its entirety.

technical field

The present invention relates to simplified organic electronic devices comprising polymer anodes with high work function.

Background technique

Organic light emitting devices, which are self-emitting devices, have advantages such as wide viewing angles, excellent contrast, fast response, high luminance, excellent driving voltage characteristics, and can provide multicolor images.

A conventional organic light emitting device includes an anode, a cathode, and an organic layer interposed between the anode and the cathode. The organic layer may include an electron injection layer (EIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and a cathode. When a voltage is applied between the anode and cathode, holes injected from the anode move to the EML via the HTL, and electrons injected from the cathode move to the EML via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons fall from an excited state to a ground state, light is emitted.

Meanwhile, many studies on renewable energy have been conducted worldwide. In this regard, organic solar cells have drawn much attention as a future energy source due to their potential to use solar energy. Compared with inorganic solar cells using silicon, organic solar cells can form thin films more efficiently and can be manufactured at low manufacturing costs, and thus can be applied to various flexible devices.

The cost of indium tin oxide (ITO) electrodes commonly used in organic light-emitting diodes and organic solar cells continues to increase due to depletion of indium, and ITO is brittle and easily broken when impacted or bent. Therefore, ITO cannot be applied to flexible devices. Although research on electrodes for replacing ITO has been conducted, the developed electrodes do not have a sufficient work function. Accordingly, a multilayer structure for smooth injection and transfer of charges is formed on the electrodes. However, this structure increases the amount of materials used to prepare the electronic device and the manufacturing cost. Therefore, there is a need to develop an organic electronic device having a simplified structure with excellent performance by using a flexible electrode with a high work function without using a hole transport/extraction auxiliary layer, and to apply the organic electronic device to flexible devices as well as conventional Tablet device.

Contents of the invention

The present invention provides simplified electronics including flexible electrodes with high conductivity and high work function.

According to one aspect of the present invention, there is provided an electronic device using an electrode having a high work function and high conductivity, the electrode comprising a conductive material having a conductivity of 0.1 S/cm or more and a low surface energy material, and having a first surface and a second surface opposite to the first surface, wherein the concentration of the low surface energy material in the second surface is greater than the concentration of the low surface energy material in the first surface, and the second surface The work functions of the two surfaces are 5.0 eV or more.

A concentration of the low surface energy material may gradually increase in a direction from the first surface to the second surface.

The low surface energy material may be a fluorinated material having at least one F.

The conductive material may include polythiophene, polyaniline, polypyrrole, polystyrene, sulfonated polystyrene, poly(3,4-ethylenedioxythiophene), self-doped conductive polymer, any derivative thereof objects, and any combination thereof.

The high work function and high conductivity electrode may further include at least one of metal nanowires, semiconductor nanowires, metal nanodots, graphene, reduced graphene oxide, and graphite.

The metal nanowires may be selected from Ag, Au, Cu, Pt, nickel silicide ( _NiSix ), metal carbon nanotubes, and any composites of at least two thereof such as alloys or core-shell structures, but are not limited thereto.

The semiconductor nanowire can be selected from Si, Ge, Si doped with B or N, Ge doped with B or N, and any composite of at least two thereof such as an alloy or a core-shell structure, but not limited to this.

The metal nanodots may be selected from Ag, Au, Cu, Pt, and any composites of at least two thereof such as alloys or core-shell structures, but are not limited thereto.

At least one moiety represented by -S(Z ₁₀₀ ) or -Si(Z ₁₀₁ )(Z ₁₀₂ )(Z ₁₀₃ ), wherein Z ₁₀₀ , Z ₁₀₁ , Z ₁₀₂ and Z ₁₀₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group.

A work function of the second surface may be in the range of 5.0eV-6.5eV. For example, the work function of the second surface may be in the range of 5.3eV-6.2eV.

The electronic device may include an organic light emitting device, an organic solar cell, an organic memory device, or an organic thin film transistor, but is not limited thereto. All types of organic electronic devices, inorganic electronic devices and energy devices can be used.

If the electronic device is composed of an ionization potential of 5.0 eV or greater (which is 0.3 eV or more greater than the work function of a typical indium tin oxide (ITO) electrode (which is in the range of about 4.7-4.9 eV) In the organic light-emitting device of the emission layer, the electrode with high work function and high conductivity according to the present invention can be used instead of the ITO anode. In this regard, the second surface of the high work function and high conductivity electrode may face the emission layer. In addition, a second surface of the high work function and high conductivity electrode may be in contact with the emission layer. Alternatively, a hole transport layer may be selectively interposed between the high work function and high conductivity electrode and the emission layer. Here, the second surface of the high work function and high conductivity electrode may be in contact with the hole transport layer. Typically, a hole injection layer and a hole transport layer are placed between the ITO anode and the emissive layer. However, due to the use of the high work function and high conductivity electrodes, HIL and/or HTL may not be formed. Therefore, a flexible organic light emitting display and a flat organic light emitting display can be manufactured using the electrode with high work function and high conductivity, and the structure of the organic light emitting device can be simplified.

Meanwhile, if the electronic device is an organic solar cell including a photoactive layer having an ionization potential of 5.0 eV or more (which is 0.3 eV or more larger than the work function of a general ITO electrode), the method according to the present invention can be used. An electrode with high work function and high conductivity replaces the ITO anode. In this regard, the second surface of the high work function and high conductivity electrode may face the photoactive layer. Here, the second surface of the high work function and high conductivity electrode may be in contact with the photoactive layer. Typically, a hole extraction layer is placed between the ITO anode and the photoactive layer. However, since the high work function and high conductivity electrode is used, the hole extraction layer may not be formed. Therefore, flexible organic solar cells and flat solar cells can be manufactured using the high work function and high conductivity electrodes, and the structure of the organic solar cells can be simplified.

Description of drawings

The above and other features and advantages of the present invention will become apparent by describing in detail exemplary embodiments thereof with reference to the accompanying drawings, in which:

1 is a schematic cross-sectional view of an electrode according to an embodiment of the present invention;

2 is a schematic cross-sectional view of an organic light emitting device according to an embodiment of the present invention;

Figure 3 schematically shows the work function of the substrate, electrode (anode) and hole transport layer (HTL) of the organic light emitting device;

4 is a schematic cross-sectional view of an organic solar cell according to an embodiment of the present invention;

5 is a schematic cross-sectional view of an organic thin film transistor (TFT) according to an embodiment of the present invention;

6 is a graph illustrating an energy spectrum of X-ray photoelectron spectroscopy (XPS), which shows the molecular concentration of the electrode 4 prepared according to Example 1 with respect to sputtering time;

7 is a graph illustrating the transmittance of electrodes 1-4 and A prepared according to Example 1 and Comparative Example A;

Figure 8 is a graph illustrating the hole mobility of electrodes 1-4 prepared according to Example 1;

9 is a graph illustrating the hole injection efficiency of electrodes 1-4 prepared according to Example 1;

10 is a graph illustrating the efficiency versus luminance of organic light emitting diodes (OLEDs) 1-4 and A-B prepared according to Example 2 and Comparative Examples 1-3;

Figure 11 is a graph illustrating brightness versus voltage for OLEDs 1-4 and A-B prepared according to Example 2 and Comparative Examples 1-3; and

12 is a graph illustrating the brightness versus time of OLEDs 1-4 and A-B prepared according to Example 2 and Comparative Examples 1-3.

detailed description

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one of" when preceding a list of elements modify the entire list of elements and do not modify the individual elements of the list.

1 is a schematic cross-sectional view of a high work function and high conductivity electrode 15 and substrate 10 according to an embodiment of the present invention.

The high work function and high conductivity electrode 15 includes a conductive material having a conductivity of 0.1 S/cm or more and a low surface energy material. The electrode 15 having a high work function and high conductivity has a first surface 15A and a second surface 15B opposite to the first surface 15A. The concentration of the low surface energy material in the second surface 15B is greater than the concentration of the low surface energy material in the first surface 15A. The second surface 15B may have a work function of 5.0 eV or more. The high work function and high conductivity electrode 15 having a thickness of 100 nm has a conductivity of 1 S/cm or more.

The "low surface energy material" used herein refers to a material capable of forming a film with low surface energy, particularly a material having a lower surface energy than the conductive material. In the composition comprising the low surface energy material and the conductive material, due to the difference in surface energy between the low surface energy material and the conductive material, phase segregation (phase separation, phasesegregation) occurs, so that the low surface energy material An upper phase is formed, and the conductive material forms a lower phase. The low surface energy material includes at least one F and may have a higher hydrophobicity than the conductive material. In addition, the low surface energy material may be a material capable of providing a higher work function than the conductive material. For example, a thin film having a thickness of 100 nm and formed of the low surface energy material may have a surface energy of 30 mN/m or less and an electrical conductivity in the range of 10 ⁻¹⁵ to 10 ⁻¹ S/cm. In addition, a thin film having a thickness of 100 nm and formed from the conductive polymer composition including the low surface energy material may have a surface energy of 30 mN/m or less and conductance in the range of 10 ^-7 to 10 ^-1 S/cm Rate.

Therefore, when the composition for forming an electrode including the conductive material and the low surface energy material is applied to the substrate 10, due to the low surface energy of the low surface energy material, the conductive material and the low surface energy material cannot Mix with each other evenly. Alternatively, the conductive material and the low surface energy material may be distributed such that the concentration of the low surface energy material gradually increases in the direction from the first surface 15A to the second surface 15B, and relatively, the conductive material The concentration gradually increases in the direction from the second surface 15B to the first surface 15A. Then, the composition for forming an electrode comprising the conductive material and the low surface energy material and applied to the substrate 10 is baked to form a high work function and high conductivity electrode 15, wherein the concentration of the low surface energy material is gradually increases in the direction from the first surface 15A to the second surface 15B.

Since the electrode 15 having a high work function and high conductivity is formed by self-organization of the conductive material and the low surface energy material by performing a one solution film-forming process, it has a single-layer structure in which the The boundary between the layer of conductive material and the layer of low surface energy material is not identifiable.

The work function of the first surface 15A of the high work function and high conductivity electrode 15 may be equal to or greater than the work function of the conductive material, and the work function of the second surface 15B of the high work function and high conductivity electrode 15 may be equal to or less than the work function of the low surface energy material, but the work function is not limited thereto.

The low surface energy material may be a material having a solubility in polar solvents of 90% or greater, such as 95% or greater. Examples of the polar solvent include water, alcohols (methanol, ethanol, n-propanol, 2-propanol, n-butanol, etc.), ethylene glycol, glycerol, dimethylformamide (DMF), dimethyl Sulfoxide (DMSO), acetone, etc., but not limited thereto.

The low surface energy material may include at least one F. For example, the low surface energy material can be a fluorinated polymer or oligomer having at least one F.

According to an embodiment of the present invention, the low surface energy material may be a fluorinated polymer having a repeating unit represented by one of the following formulas 1-3.

Formula 1

In Formula 1, a is a number from 0 to 10,000,000;

b is a number from 1 to 10,000,000; and

Q ₁ is -[OC(R ₁ )(R ₂ )-C(R ₃ )(R ₄ )] _c -[OCF ₂ CF ₂ ] _d -R ₅ , -COOH or -OR _f -R ₆ ;

wherein R ₁ x , R ₂ , R ₃ and R ₄ are each independently -F, -CF ₃ , -CHF ₂ or -CH ₂ F;

c and d are each independently a number from 0-20;

R _f is -(CF ₂ ) _z -, where z is an integer from 1 to 50, or -(CF ₂ CF ₂ O) _z -CF ₂ CF ₂ -, where z is an integer from 1 to 50;

R ₅ and R ₆ are each independently -SO ₃ M, -PO ₃ M ₂ or -CO ₂ M;

Where M is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _w NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ or CH ₃ (CH ₂ ) _w CHO ⁺ , wherein w is an integer of 0-50.

Formula 2

In formula 2, Q ₂ is a hydrogen atom, a substituted or unsubstituted C ₆ -C ₆₀ aryl group, or -COOH;

Q ₃ is a hydrogen atom, or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group;

Q ₄ is -O-(CF ₂ ) _r -SO ₃ M, -O-(CF ₂ ) _r -PO ₃ M ₂ , -O-(CF ₂ ) _r -CO ₂ M or -CO-NH-(CH ₂ ) _s -(CF ₂ ) _t -CF ₃ ;

wherein r, s and t are each independently a number from 0 to 20; and

Where M is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _w NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ or CH ₃ (CH ₂ ) _w CHO ⁺ , wherein w is an integer of 0-50.

Formula 3

In formula 3, 0≤m<10,000,000 and 0<n≤10,000,000;

x and y are each independently a number from 0 to 20; and

Y is -SO ₃ M, -PO ₃ M ₂ or -CO ₂ M;

Where M is Na ⁺ , K ⁺ , Li ⁺ , H ⁺ , CH ₃ (CH ₂ ) _w NH ₃ ⁺ , NH ₄ ⁺ , NH ₂ ⁺ , NHSO ₂ CF ₃ ⁺ , CHO ⁺ , C ₂ H ₅ OH ⁺ , CH ₃ OH ⁺ or CH ₃ (CH ₂ ) _w CHO ⁺ , wherein w is an integer of 0-50.

For example, the low surface energy material may be a fluorinated polymer including a repeating unit represented by Formula 1, but is not limited thereto.

For example, the low surface energy material is a fluorinated polymer comprising repeating units represented by formula 1, wherein a is a number from 100 to 10000, b is a number from 50 to 1000, and Q ₁ is -[OC(R ₁ )(R ₂ )-C(R ₃ )(R ₄ )] _c -[OCF ₂ CF ₂ ] _d -R ₅ .

For example, the low surface energy material may be a fluorinated polymer comprising repeating units represented by formula 1, wherein a is a number from 100 to 10000, b is a number from 50 to 1000, Q ₁ is -[OC(R ₁ )(R ₂ )-C(R ₃ )(R ₄ )] _c- [OCF ₂ CF ₂ ] _d -R ₅ , wherein c is the number of 1-3, R ₁ , R ₂ and R ₃ are-F, R ₄ is -CF ₃ , d is a number of 1-3, and R ₅ is -SO ₃ M, but the low surface energy material is not limited thereto.

Meanwhile, the low surface energy material may be a fluorinated silane-based material represented by Formula 10 below.

Formula 10

XM ^f _n -M ^h _m -M ^a _r -(G) _p

In Equation 10,

X is a terminal group;

M ^f is a unit derived from a fluorinated monomer or a fluorinated C ₁ -C ₂₀ alkylene group prepared by the condensation reaction of perfluoropolyether alcohols, polyisocyanates and isocyanate-reactive non-fluorinated monomers:

^M is a unit derived from a non-fluorinated monomer;

M ^a is a unit having a silyl group represented by -Si(Y ₄ )(Y ₅ )(Y ₆ ),

Wherein, Y ₄ , Y ₅ and Y ₆ are each independently a halogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a hydrolyzable substituent, wherein at least one of Y ₄ , Y ₅ and Y ₆ is a hydrolyzable substituent,

G is a monovalent organic group including a chain transfer agent;

n is a number from 1 to 100;

m is a number from 0 to 100;

r is a number from 0-100;

where n+m+r≥2; and

p is a number from 0-10.

For example, X can be a halogen atom, M ^f can be a fluorinated C ₁ -C ₁₀ alkylene group, M ^h can be a C ₂ -C ₁₀ alkylene group, Y ₄ , Y ₅ and Y ₆ can each be independently Halogen atoms (Br, Cl, F, etc.), and p may be 0. For example, the fluorinated silane-based material represented by Formula 10 may be CF ₃ CH ₂ CH ₂ SiCl ₃ , but is not limited thereto.

The fluorinated silane-based material represented by Formula 10 is described in US Patent No. 7,728,098, the disclosure of which is incorporated herein by reference in its entirety.

The conductive material may be a conductive polymer having a high electrical conductivity of 0.1 S/cm or more, such as 1 S/cm or more.

For example, the conductive material may include polythiophene, polyaniline, polypyrrole, polystyrene, sulfonated polystyrene, poly(3,4-ethylenedioxythiophene), self-doped conductive polymers, and Any derivatives and combinations thereof. The derivatives may include various sulfonic acids.

For example, the conductive material may include polyaniline/dodecylbenzenesulfonic acid (Pani:DBSA, see formula below), poly(3,4-ethylenedioxythiophene)/poly(4-sulfostyrene) (PEDOT:PSS, refer to the following formula), polyaniline/camphorsulfonic acid (Pani:CSA), or polyaniline/poly(4-sulfonylstyrene) (PANI:PSS), but not limited thereto.

Here, R can be H or C ₁ -C ₁₀ alkyl.

The self-doping conductive polymer may have a degree of polymerization in the range of 10-10,000,000 and may include repeating units represented by Formula 13 below.

Formula 13

In formula 13, 0<m<10,000,000, 0<n<10,000,000, 0≤a≤20 and 0≤b≤20;

At least one of R ₁ , R ₂ , R ₃ , R' ₁ , R' ₂ , R' ₃ and R' ₄ includes an ionic group, and A, B, A' and B' are each independently selected from C, Si , Ge, Sn and Pb;

R ₁ , R ₂ , R ₃ , R' ₁ , R' ₂ , R' ₃ and R' ₄ are each independently selected from a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted amino group, a cyano group, a substituted or Unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₁ -C ₃₀ alkoxy, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aryl Alkyl, substituted or unsubstituted C ₆ -C ₃₀ aryloxy, substituted or unsubstituted C ₂ -C ₃₀ heteroaryl, substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkyl, substituted or unsubstituted Substituted C ₂ -C ₃₀ heteroaryloxy, substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₁ -C ₃₀ alkyl ester groups, and substituted or unsubstituted C ₆ -C ₃₀ aryl ester groups, wherein a hydrogen atom or a halogen atom is selectively attached to the carbon of the repeating unit of formula 13;

R is a conjugated conductive polymer chain _; and

X and X' are each independently selected from a single bond, O, S, substituted or unsubstituted C ₁ -C ₃₀ alkylene, substituted or unsubstituted C ₁ -C ₃₀ heteroalkylene, substituted or unsubstituted C ₆ -C ₃₀ arylene, substituted or unsubstituted C ₆ -C ₃₀ arylene alkyl (C ₆ -C ₃₀ arylalkylene), substituted or unsubstituted C ₂ -C ₃₀ heteroarylene substituted or unsubstituted C ₂ -C ₃₀ heteroarylalkylene (C ₂ -C ₃₀ heteroarylalkylene), substituted or unsubstituted C ₅ -C ₂₀ cycloalkylene, and substituted or Unsubstituted C ₅ -C ₃₀ heterocycloalkylene in which a hydrogen atom or a halogen atom is selectively attached to the carbon of the repeating unit of Formula 13.

For example, the ionic groups may be selected from: anionic groups selected from PO ₃ ^2- , SO ₃ ^- (SO ₃ ^2- ), COO ^- , I ^- and CH ₃ COO ^- ; selected from Na ⁺ , K ⁺ , Li ⁺ , Mg ²⁺ , Zn ²⁺ and Al ³⁺ metal ions; and organic ions selected from H ⁺ , NH ₄ ⁺ and CH ₃ (-CH ₂ -) _n O ⁺ , wherein n is 1-50 of natural numbers. The ionic group may further include a cationic group matching the anionic group.

For example, in the self-doping conductive polymer of formula 13, at least one of R ₁ , R ₂ , R ₃ , R' ₁ , R' ₂ , R' ₃ and R' ₄ may be fluorine or a group substituted with fluorine group, but the self-doping conductive polymer is not limited thereto.

Examples of unsubstituted alkyl groups include linear or branched alkyl groups such as methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl. One or more hydrogen atoms in the alkyl group can be substituted by: a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted amino group (-NH ₂ , -NH(R) or -N(R') (R"), wherein R, R' and R" are each independently C ₁ -C ₁₀ alkyl), amidino, hydrazine, hydrazone, carboxyl, sulfonic acid, phosphoric acid, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ alkenyl (C ₂ -C ₂₀ alkenyl), C ₁ -C ₂₀ alkynyl (C ₂ -C ₂₀ alkynyl), C ₁ -C ₂₀ heteroalkyl , C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ arylalkyl (C ₇ -C ₂₀ aralkyl), C ₆ -C ₂₀ heteroaryl, or C ₆ -C ₂₀ heteroarylalkyl.

A heteroalkyl group is a group formed by replacing one or more carbon atoms, such as 1 to 5 carbon atoms, of the main chain of the alkyl group with a heteroatom such as O, S, N or P.

Aryl refers to a carbocyclic aromatic system comprising one or more aromatic rings joined or fused together by a pendant process. Examples of aryl groups include phenyl, naphthyl and tetrahydronaphthyl. One or more hydrogen atoms of the aryl group may be substituted with the same substituents as in the alkyl group.

Heteroaryl means a 5-30 membered aromatic ring system having 1, 2 or 3 heteroatoms selected from N, O, P and S and the remaining ring atoms being carbon, wherein the rings are attached by pendant means or Fused together. In addition, one or more hydrogen atoms of the heteroaryl group may be substituted with the same substituents as in the alkyl group.

Alkoxy refers to the group -O-alkyl wherein said alkyl is as defined above. Examples of alkoxy include methoxy, ethoxy, propoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, and hexyloxy. One or more hydrogen atoms of the alkoxy group may be substituted with the same substituents as in the alkyl group.

Heteroalkoxy means an alkoxy group in which at least one _heteroatom such as O, S _or N is present in the alkyl chain, and examples of _heteroalkoxy include _{CH3CH2OCH2CH2O-} , _{C4H 9} OCH ₂ CH ₂ OCH ₂ CH ₂ O- and CH ₃ O(CH ₂ CH ₂ O) _n H, CH ₃ O(CH ₂ CH ₂ O) _n -.

Arylalkyl means a group formed by substituting a lower alkyl group such as methyl, ethyl, propyl, etc. for some of the hydrogen atoms of the aryl group defined above. For example, arylalkyl can be benzyl, phenethyl, and the like. One or more hydrogen atoms of the arylalkyl group may be substituted with the same substituents as in the alkyl group.

Heteroarylalkyl refers to a group formed by replacing some of the hydrogen atoms of a heteroaryl with a lower alkyl. In the heteroarylalkyl group, the heteroaryl group is as defined above. One or more hydrogen atoms of the heteroarylalkyl group may be substituted with the same substituents as in the alkyl group.

Aryloxy refers to the group -O-aryl, wherein the aryl is as defined above. Examples of the aryloxy group include phenoxy, naphthyloxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy and indenyloxy. One or more hydrogen atoms of the aryloxy group may be substituted with the same substituents as in the alkyl group.

Heteroaryloxy refers to the group -O-heteroaryl, wherein said heteroaryl is as defined above.

Examples of heteroaryloxy include benzyloxy and phenethoxy. One or more hydrogen atoms of the heteroaryloxy group may be substituted with the same substituents as in the alkyl group.

Cycloalkyl refers to a monovalent monocyclic ring system having 5-30 carbon atoms. One or more hydrogen atoms of the cycloalkyl group may be substituted with the same substituents as in the alkyl group.

Heterocycloalkyl refers to a 5-30 membered monovalent monocyclic ring system having 1, 2 or 3 heteroatoms selected from N, O, P or S and the remaining ring atoms being C. One or more hydrogen atoms of the heterocycloalkyl group may be substituted with the same substituents as in the alkyl group.

Alkyl ester group refers to a functional group in which an alkyl group is combined with an ester group, wherein the alkyl group is as defined above.

A heteroalkyl ester group refers to a functional group in which a heteroalkyl group is combined with an ester group, wherein the heteroalkyl group is as defined above.

An aryl ester group refers to a functional group in which an aryl group is combined with an ester group, wherein the aryl group is as defined above.

A heteroaryl ester group refers to a functional group in which a heteroaryl group is combined with an ester group, wherein the heteroaryl group is as defined above. Amino refers to -NH ₂ , -NH(R) or -N(R')(R"), wherein R, R' and R" are each independently C ₁ -C ₁₀ alkyl.

The halogen atom may be fluorine, chlorine, bromine, iodine or astatine, eg fluorine.

The high work function and high conductivity electrode 15 may further include metal nanowires in addition to the aforementioned conductive material and low surface energy material. The metal nanowires may improve electrical conductivity, optical properties, and mechanical strength of the high work function and high electrical conductivity electrode 15 . The metal nanowires can be selected from, for example, Ag, Au, Cu, Pt, nickel silicide ( _NiSix ), metal carbon nanotubes, and any composites of at least two thereof such as alloys or core-shell structures, but are not limited thereto .

The high work function and high conductivity electrode 15 may further include at least one of graphene flakes and dots, reduced graphene oxide, and graphite, in addition to the aforementioned conductive material and low surface energy material.

The high work function and high conductivity electrode 15 may further include semiconductor nanowires in addition to the conductive material and low surface energy material. The semiconductor nanowires and metal nanowires can further improve the electrical conductivity and optical properties of the high work function and high electrical conductivity electrode 15 . The semiconductor nanowire can be selected from Si, Ge, Si doped with B or N, Ge doped with B or N, and any composite of at least two thereof such as an alloy or a core-shell structure, but not limited to this.

The metal nanowires and semiconductor nanowires may have a diameter in a range of 5 nm-100 nm and a length in a range of 500 nm-100 μm. However, the diameter and length of the metal nanowires and semiconductor nanowires may vary according to methods of manufacturing the metal nanowires and semiconductor nanowires.

The high work function and high conductivity electrode 15 may further include metal nanodots in addition to the above-mentioned conductive material and low surface energy material. The metal nanodots may be selected from Ag, Au, Cu, Pt, and any composites of at least two thereof such as alloys or core-shell structures, but are not limited thereto.

At least one moiety represented by -S(Z ₁₀₀ ) and -Si(Z ₁₀₁ )(Z ₁₀₂ )(Z ₁₀₃ ), wherein Z ₁₀₀ , Z ₁₀₁ , Z ₁₀₂ and Z ₁₀₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group. The moieties represented by -S(Z ₁₀₀ ) and -Si(Z ₁₀₁ )(Z ₁₀₂ )(Z ₁₀₃ ) are self-assembled moieties by which the metal nanowires, semiconductor nanowires and metal nanowires can be improved, respectively. The binding force within the nanodots may improve the binding force between the metal nanowires, semiconductor nanowires or metal nanodots and the substrate 10 . Therefore, the electrical characteristics and mechanical strength of the high work function and high conductivity electrode 15 can be improved.

The metal nanowires, semiconductor nanowires and/or metal nanodots may be uniformly dispersed in the electrode 15 with high work function and high conductivity, or non-uniformly dispersed in a specific portion of the electrode 15 with high work function and high conductivity. in the area.

For example, the metal nanowires can be formed only on the first surface 15A of the high work function and high conductivity electrode 15 by forming the metal nanowires on the substrate 10 using known methods, which will include the conductive A composition for forming an electrode of a material and a low surface energy material is applied on the substrate 10 on which the metal nanowires are formed, and the structure is baked.

The metal nanowires, semiconductor nanowires and metal nanodots may be combined with at least one of the conductive material and the low surface energy material contained in the electrode 15 having a high work function and high conductivity, that is, physically and/or chemically combined to form a compound.

The total content of the low surface energy material in the high work function and high conductivity electrode 15 may be in the range of 10 parts by weight to 500 parts by weight, such as 20 parts by weight to 400 parts by weight, based on 100 parts by weight of the conductive material, But not limited to this. If the content of the low surface energy material is within the above range, the high work function and high conductivity electrode 15 may have high conductivity and high work function of the second surface 15B.

If the high work function and high conductivity electrode 15 is used as a transparent electrode, the thickness L of the high work function and high conductivity electrode 15 may be in the range of 20nm-500nm, for example, 50nm-200nm. If the thickness L of the high work function and high conductivity electrode 15 is within the above range, work function, transmittance, and flexibility may be improved. At the same time, if the electrode 15 with high work function and high conductivity is used as a reflective electrode and/or wire, the thickness L of the electrode 15 with high work function and high conductivity can be in the range of 20nm-100μm, such as 500nm-5μm . If the thickness of the high work function and high conductivity electrode 15 is within the above range, the work function and conductivity can be improved.

The electrode 15 having a high work function and high conductivity as described above can be formed by applying a composition for forming an electrode including the conductive material, the low surface energy material, and a solvent to the substrate 10, and heat-treating the electrode 15. said composition.

First, the substrate 10 may be any substrate commonly used in semiconductor processes. For example, substrate 10 may include glass, sapphire, silicon, silicon oxide, metal foils such as copper and aluminum foils, steel such as stainless steel, metal oxides, polymer substrates, and any combination of at least two thereof. Examples of the metal oxide include aluminum oxide, molybdenum oxide, indium tin oxide, tin oxide, and indium tin oxide, and examples of the polymer base include polyimide resins (polypyromellimid, kapton ) foil, polyethersulfone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET) , polyphenylene sulfide (PPS), polyallylate (polyallylate), polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), etc., but examples Not limited to this.

For example, substrate 10 may be a polymer substrate as described above, but is not limited thereto.

Then, a composition for forming an electrode including the conductive material, the low surface energy material, and a solvent is applied to the substrate 10 .

In the composition for forming an electrode, the conductive material and the low surface energy material are as defined above.

In the composition for forming an electrode, the solvent may be any solvent that is miscible with the conductive material and the low surface energy material and that can be removed by heat treatment. The solvent may be a polar solvent, and examples of the solvent include water, alcohols such as methanol, ethanol, n-propanol, 2-propanol, and n-butanol, polar organic solvents such as ethylene glycol, glycerol, di Methylformamide (DMF) and dimethyl sulfoxide (DMSO), or any combination of at least two thereof.

The solvent may be a mixture of at least two different materials. Alternatively, the solvent may include the polar organic solvent. For example, the solvent may be a polar organic solvent, a mixture of water and alcohol, a mixture of water and a polar organic solvent, a mixture of alcohol and a polar organic solvent, or a mixture of water, alcohol and a polar organic solvent, and other Change is possible.

Examples of the polar organic solvent include ethylene glycol, glycerin, DMF, DMSO, and any combination of at least two thereof, but examples are not limited thereto.

Since the polar organic solvent improves the aggregation and crystallization ability of the conductive polymer contained in the electrode-forming composition, it is possible to control or improve the electrode-forming composition and the The conductivity of the electrode.

If the solvent includes a polar organic solvent, the content of the polar organic solvent may range from 1 to 30% by weight based on 100% by weight of the composition for forming an electrode, but is not limited thereto.

For example, the electrode 15 having a high work function and high conductivity is not formed by separately forming a conductive material layer and a low surface energy material layer. On the contrary, since the conductive material and the low surface energy material self-align to form a concentration gradient due to the difference in surface energy, the electrode 15 having a high work function and high conductivity is obtained by using a one layer-forming process including ) formation: applying a composition for forming an electrode including the conductive material, a low surface energy material, and a solvent to the substrate 10 and heat-treating the composition. Therefore, its manufacturing method is simple. Thus, the electrode 15 with high work function and high conductivity can be effectively used in the fabrication of large-area electronic devices.

The electrode 15 with high work function and high conductivity can be used in various electronic devices. The high work function and high conductivity electrode 15 has flexibility, which distinguishes it from ITO. Therefore, flexible electronic devices can be fabricated by using flexible structures. Therefore, the electronic device can have flexibility. The flexible substrate may be the above-mentioned polymer substrate, but is not limited thereto.

The electronic device may be a device having various known structures and performing various functions, such as an organic light emitting device, an organic solar cell, an organic memory device, or an organic thin film transistor (TFT).

The electronic device can be used in various electronic devices such as display devices, lighting lamps, and semiconductor chips.

2 is a schematic cross-sectional view of an organic light emitting device 100 including an electrode 120 with a high work function and high conductivity. The organic light emitting device 100 of FIG. 2 includes a substrate 110, a high work function and high conductivity electrode 120, a hole transport layer (HTL) 130, an emission layer (EML) 140, an electron transport layer (ETL) 150, an electron injection layer ( EIL) 160, and a second electrode 170. When a voltage is applied to the high work function and high conductivity electrode 120 and the second electrode 170 of the organic light emitting device 100, holes injected from the high work function and high conductivity electrode 120 move to the EML 140 via the HTL 130, and Electrons injected from the second electrode 170 move to the EML 140 via the ETL 150 and the EIL 160 . The holes and electrons recombine in the EML 140 to generate excitons. When the excitons fall from an excited state to a ground state, light is emitted. The substrate 110 may be disposed under the electrode 120 having a high work function and high conductivity. The high work function and high conductivity electrode 120 may serve as an anode, and the second electrode 170 may serve as a cathode.

The substrate 110 may be the above-mentioned substrate. For example, substrate 110 may be a flexible substrate, such as a polymeric substrate as described above.

The high work function and high conductivity electrode 120 is defined as described above with respect to the high work function and high conductivity electrode 15 .

The organic light emitting device 100 may not include a hole injection layer (HIL).

The film conductivities of conventional HILs formed using conductive polymer compositions such as PEDOT:PSS and PANI:PSS range from about 10 ⁻⁶ S/cm to about 10 ⁻² S/cm. For example, PEDOT:PSS of CLEVIOUS ^™ P VP AI4083 (Heraeous GmbH from HC Starck GmbH) has a conductivity of 10 ⁻³ S/cm, and PEDOT:PSS of CLEVIOUS ^™ P VP CH8000 (Heraeous GmbH from HC Starck GmbH) has a conductivity of 10 ⁻ Conductivity of ⁶ S/cm. However, since a conductive polymer should have a conductivity of 0.1 S/cm or more for forming an electrode, PEDOT:PSS, which is generally used to form a conventional HIL, cannot be used. In addition, the conductive material having a conductivity of 0.1 S/cm or more according to the current embodiment cannot be used to form the HIL because crosstalk may occur between pixels of the organic light emitting device. Therefore, conductive polymers generally used to form HILs have been selected from materials having a conductivity of 10 ⁻² S/cm or less and a work function higher than that of ITO generally used in this field, thereby facilitating hole injection .

FIG. 3 schematically shows the work function of the high work function and high conductivity electrode 120 and the HTL 130 .

As shown in FIG. 3 , the work function of the high work function and high conductivity electrode 120 may have a range from the first surface 120A of the high work function and high conductivity electrode 120 to the high work function and high conductivity electrode 120. A variable in the gradient of the second surface 120B increase. The work function of the first surface 120A of the high work function and high conductivity electrode 120 is Y ₁ eV, and the work function of the second surface 120B is Y ₂ eV, where Y ₁ <Y ₂ . Therefore, holes can efficiently move from the high work function and high conductivity electrode 120 to the HTL 130 without the need for a HIL between the high work function and high conductivity electrode 120 and the HTL 130 . That is, the electrode 120 having a high work function and high conductivity functions as an anode and an HIL. Accordingly, the organic light emitting device 100 including the electrode 120 having a high work function and high conductivity may have excellent efficiency, high brightness, and long lifetime without forming an HIL. As a result, the manufacturing cost of the organic light emitting device 100 may be reduced.

The work function of the HTL 130 is ZeV, where Z is a real number of 5.4-5.6, but the work function of the HTL 130 is not limited thereto.

The work function Y ₁ of the first surface 120A of the high work function and high conductivity electrode 120 is equal to or greater than the work function of the conductive material. For example, the work function Y ₁ may be in the range of 4.6-5.2, such as 4.7-4.9. The work function Y ₂ of the second surface 120B of the high work function and high conductivity electrode 120 is equal to or smaller than the work function of the low surface energy material. For example, _Y2 may be in the range of 5.0-6.5, such as, but not limited to, 5.3-6.2.

Since the organic light emitting device 100 does not include the HIL, the second surface 120B of the high work function and high conductivity electrode 120 may be in contact with the HTL 130 .

The HTL 130 may be formed by using any known method selected from vacuum deposition, spin coating, casting, Langmuir-Brodgett (LB) technique, and the like. When the HTL 130 is formed by using vacuum deposition, deposition conditions may vary depending on the compound used to form the HTL 130, and the structure and thermal properties of the HTL 130 to be formed. For example, the conditions of vacuum deposition may include a deposition temperature ranging from 100 to 500°C, a range from 10 ⁻¹⁰ to 10 ⁻³ . Torr pressure, and the range is /sec deposition rate. Meanwhile, when the HTL 130 is formed by using spin coating, coating conditions may vary depending on the compound used to form the HTL 130, and the structure and thermal properties of the HTL 130 to be formed. For example, spin coating conditions may include a coating speed ranging from 2000 to 5000 rpm, and a heat treatment temperature ranging from 80 to 200° C. for removing a solvent after coating.

The material used to form the HTL 130 may be selected from materials capable of transporting holes more efficiently than injecting holes. The material used to form HTL 130 can be any known hole transport material. Examples of the material include amine derivatives having aromatic dense rings such as N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine (NPB), N-phenylcarbazole and N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), and based on triphenylamine materials such as 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA). Among these materials, TCTA can not only transport holes but also suppress the diffusion of excitons from the EML 140 .

The thickness of the HTL 130 may be in the range of 5-100 nm, for example, 10-60 nm. When the thickness of the HTL 130 is within this range, the HTL 130 may have excellent hole transport properties without increasing the driving voltage.

The EML 140 may be formed by using any known method selected from vacuum deposition, spin coating, casting, LB techniques, and the like. In this regard, deposition and coating conditions may be similar to those used to form HTL 130, although deposition and coating conditions may vary depending on the compounds used to form EML 140, and the structural and thermal properties of EML 140 to be formed.

The EML 140 has an ionization potential 0.3 eV or more greater than the work function of general indium tin oxide such as non-surface-treated indium tin oxide. In this regard, the work function of ITO and the ionization potential of EML140 were measured under the same conditions using the same equipment.

The EML 140 may be formed of an emission material or may include a host and a dopant.

Examples of such hosts include Alq ₃ , 4,4'-N,N'-dicarbazole-biphenyl (CBP), 9,10-di(naphthalene-2-yl)anthracene (ADN), TCTA, 1, 3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis(naphthalene-2-yl)anthracene (TBADN), E3 (see below formula) and BeBq ₂ (see formula below), but not limited thereto. NPB, which is a material for forming the HTL 130, may also be used as a host if necessary.

Meanwhile, examples of known red dopants include rubrene (5,6,11,12-tetraphenylnaphthocene), (PtOEP), Ir(piq) ₃ , and Btp ₂ Ir(acac), But not limited to this.

Examples of known green dopants include, but are not limited to, Ir(ppy) ₃ (ppy=phenylpyridine), Ir(ppy) ₂ (acac), Ir(mpyp) ₃ and 10-(2-benzothiazole Base)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyronyl[6,7-8-i, j] Quinazin-11-one (C545T), see formula below.

C545T

Meanwhile, examples of known blue dopants include F ₂ Irpic, (F ₂ ppy) ₂ Ir(tmd), Ir(dfppz) ₃ , ter-fluorene, 4,4'-bis(4 - Di-p-tolylaminostyryl)biphenyl (DPAVBi), and 2,5,8,11-tetra-tert-butylperylene (TBP), but not limited thereto.

The thickness of the EML 140 may be in the range of 10-100 nm, for example, 10-60 nm. When the thickness of the EML 140 is within the above range, the EML 140 may have excellent light emitting characteristics without increasing the driving voltage.

A hole blocking layer (HBL) (not shown in FIG. 2 ) prevents triplet excitons or holes of the EML 140 (if the EML 140 includes a phosphorescent compound) from diffusing into the second electrode 170 . The HBL may be formed on the EML 140 by using any known method such as vacuum deposition, spin coating, casting, and LB techniques. In this regard, deposition and coating conditions may be similar to those used to form HTL 130, although deposition and coating conditions may vary depending on the compounds used to form the HBL, as well as the structural and thermal properties of the HBL to be formed.

The hole blocking material can be any known hole blocking material. For example, oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives can be used to form HBL.

The thickness of the HBL may be in the range of about 5 nm to about 100 nm, such as about 10 nm to about 30 nm. When the thickness of the HBL is within the above range, the HBL may have excellent hole blocking properties without increasing the driving voltage.

The ETL 150 may be formed on the EML 140 or the HBL by using any known method selected from vacuum deposition, spin coating, casting, LB techniques, and the like. In this regard, deposition and coating conditions may be similar to those used to form HTL 130, although deposition and coating conditions may vary depending on the compounds used to form ETL 150, and the structural and thermal properties of ETL 150 to be formed.

The material used to form the ETL 150 can be any known electron transport material, for example, tris(8-quinolinolato)aluminum (Alq ₃ ), TAZ, 4,7-diphenyl-1,10-phenanthroline (Bphen), BCP, BeBq ₂ and BAlq.

The thickness of the ETL 150 may be in the range of about 10 to about 100 nm, for example, about 20 to about 50 nm. When the thickness of the ETL 150 is within the above range, the ETL 150 may have excellent electron transport properties without increasing the driving voltage.

EIL 160 may be formed on ETL 150 . The material used to form the EIL 160 may be any known electron injection material such as LiF, NaCl, CsF, Li ₂ O, BaO, BaF ₂ , and lithium quinolate (Liq). Deposition conditions may be similar to those used to form HTL 130, although deposition conditions may vary depending on the compound used to form EIL 160.

The thickness of the EIL 160 may range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 5 nm. When the thickness of the EIL 160 is within the above range, the EIL 160 may have satisfactory electron injection properties without increasing the driving voltage.

The second electrode 170 may be a cathode, which is an electron injection electrode. Metals, alloys, conductive compounds, or any combination thereof may be used to form the second electrode 170 . In this regard, the second electrode 170 may be made of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), magnesium (Mg)-indium (In), Magnesium (Mg)-silver (Ag) etc. are formed. ITO, IZO, etc. can also be used to prepare top-emitting light-emitting diodes.

The organic light emitting device 100 can have a very high hole injection capability without HIL by using the high work function and high conductivity electrode 120 as an anode, and can prevent electrons from being injected into the high work function and high conductivity electrode through the HTL 130 The substrate 120 has excellent electrical characteristics, and can be flexible by using a flexible substrate as the substrate 110 .

The organic light emitting device 100 of FIG. 2 has a structure in which the HTL 130 is interposed between the high work function and high conductivity electrode 120 and the EML 140 . However, the second surface 120B of the high work function and high conductivity electrode 120 may be in contact with the EML 140 without forming the HTL 130, and other changes thereof are possible.

4 is a schematic cross-sectional view of an organic solar cell 200 including a high work function and high conductivity electrode 220 according to an embodiment of the present invention.

The organic solar cell 200 of FIG. 4 includes a substrate 210 , an electrode 220 with high work function and high conductivity, a photoactive layer 230 , an electron accepting layer 240 , and a second electrode 250 . Light reaching the organic solar cell 200 is split into holes and electrons in the photoactive layer 230 . Electrons move to the second electrode 250 through the electron accepting layer 240 , and holes move to the electrode 220 having a high work function and high conductivity.

Substrate 210 is defined as described above with respect to substrate 110 . Meanwhile, the high work function and high conductivity electrode 220 is defined as described above with respect to the high work function and high conductivity electrode 15 .

The photoactive layer 230 may include a material capable of splitting light into holes and electrons. For example, the photoactive layer 230 may include a p-type organic semiconductor material or an n-type organic semiconductor material. For example, the photoactive layer 230 may include poly(3-hexylthiophene) and phenyl-C61-butyric acid methyl ester (PCMB), but is not limited thereto.

The photoactive layer 230 has an ionization potential 0.3 eV or more greater than the work function of general indium tin oxide such as non-surface-treated indium tin oxide. In this regard, the work function of indium tin oxide and the ionization potential of the photoactive layer 230 were measured under the same conditions using the same equipment.

The electron accepting layer 240 may include a material capable of accepting electrons, for example, the material used to form the EIL 160 of the organic light emitting diode 100 as described above.

The second electrode 250 may be a cathode, which is an electron injection electrode. Metals, alloys, conductive compounds, or any combination thereof with a relatively low work function may be used to form the second electrode 250 . In this regard, the second electrode 250 may be made of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), magnesium (Mg)-indium (In), Magnesium (Mg)-silver (Ag) etc. are formed.

Since the organic solar cell 200 includes the electrode 220 with a high work function and high conductivity, the holes generated in the photoactive layer 230 can efficiently move to the electrode 220 with a high work function and high conductivity without the need for high work function and high conductivity. A hole extraction layer is formed between the high-conductivity electrode 220 and the photoactive layer 230 . Therefore, excellent electrical characteristics can be obtained. The hole extraction layer may include conductive polymers such as PEDOT:PSS and PANI:PSS commonly used in HILs of organic light-emitting devices, and the conductivity of the PEDOT:PSS film and the PANI:PSS film may be within 10 ⁻⁶ S/cm-10 ^-2 S/cm range.

The organic light emitting device and the organic solar cell have been described with reference to FIGS. 2 and 4, but are not limited thereto. For example, the high work function and high conductivity electrode 15 of FIG. 1 may also be used as a cathode of the organic light emitting device 100 and/or the organic solar cell 200 . If the electrode 15 with high work function and high conductivity is used as the cathode of the organic light emitting device 100 and/or the organic solar cell 200, the second surface 15B of the electrode 15 with high work function and high conductivity may be arranged to face the organic light emitting device EML 140 of 100 and/or photoactive layer 230 of organic solar cell 200 . For example, when the cathode 170 of the organic light emitting device 100 in FIG. 2 is an electrode 15 with a high work function and high conductivity, the second surface 15B of the electrode 15 with a high work function and high conductivity has a relatively high low surface energy The surface of the material concentration may be arranged to face the EIL 160 arranged under the cathode 170, and other variations thereof are possible. In this regard, a high work function and high conductivity electrode 15 serving as the cathode 170 may be formed on the base film and transferred onto the EIL 160 by using, for example, a laser induced thermal imaging (LITI) method or a transfer method.

In addition, when the electrode 15 with high work function and high conductivity is used as the cathode 170 , the second surface 15B may face the opposite side of the photoactive layer 230 .

In addition, the electrode 15 having a high work function and high conductivity may be used for an inverted organic light emitting diode (OLED) or an organic photovoltaic device (OPV). In an inverted OLED or OPV, a HIL (OLED) or a hole extraction layer (OPV) may be provided under a high work function and high conductivity electrode 15, and an EIL or an electron accepting layer may be provided on an anode formed on a substrate superior.

5 is a schematic cross-sectional view of an organic thin film transistor (TFT) 300 including an electrode with a high work function and high conductivity.

The organic TFT 300 of FIG. 5 includes a substrate 311, a gate electrode 312, an insulating layer 313, an organic semiconductor layer 315, and source and drain electrodes 314a and 314b. The gate electrode 312 and at least one of the source and drain electrodes 314 a and 314 b may be the high work function and high conductivity electrode 15 as described above.

Base 311 is defined as described above with respect to base 110 .

A gate electrode 312 having a predetermined pattern is formed on the substrate 311 . The gate electrode 312 may be the high work function and high conductivity electrode 15 as described above. Alternatively, the gate electrode 312 may be made of a metal such as gold (Au), silver (Ag), copper (Cu), nickel (Ni), platinum (Pt), palladium (Pd), aluminum (Al), and molybdenum (Mo), or Metal alloys such as Al:Nd and Mo:W are formed, but are not limited thereto.

An insulating layer 313 is formed on the gate electrode 312 to cover the gate electrode 312 . The insulating layer 313 may include inorganic materials such as metal oxides or metal nitrides, organic materials such as flexible organic polymers, or various other materials.

The organic semiconductor layer 315 is formed on the insulating layer 313 . The organic semiconductor layer 315 may include pentacene, tetracene, anthracene, naphthalene, α-6-thiophene, α-4-thiophene, perylene and its derivatives, rubrene and its derivatives, coronene and its derivatives , perylene tetracarboxylic acid diimide and its derivatives, perylene tetracarboxylic dianhydride and its derivatives, polythiophene and its derivatives, poly(p-phenylene vinylene) and its derivatives, poly( p-phenylene) and its derivatives, polyfluorene and its derivatives, polythiophene vinylidene and its derivatives, polythiophene-heterocyclic aromatic copolymer and its derivatives, naphthalene oligoacene (oligoacene) and its derivatives α-5-thiophene oligothiophene and its derivatives, metal-containing or non-metallic phthalocyanine and its derivatives, pyromellitic dianhydride and its derivatives, or pyromellitic diimide and derivatives thereof, but the organic semiconductor layer 315 is not limited thereto.

Source and drain electrodes 314a and 314b are formed on the organic semiconductor layer 315, respectively. As shown in FIG. 5, the source and drain electrodes 314a and 314b may overlap a portion of the gate electrode 312, but are not limited thereto. The source and drain electrodes 314a and 314b may be the high work function and high conductivity electrodes 15 as described above. Alternatively, in consideration of the work function of the material used to form the organic semiconductor layer 315, the source and drain electrodes 314a and 314b may include a noble metal having a work function of 5.0 eV or more, such as gold (Au), palladium (Pd), Platinum (Pt), nickel (Ni), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium (Os), or a combination of at least two thereof.

The electronic device has been described above with reference to FIGS. 2 to 5 , but is not limited thereto.

Example

Embodiment 1: the preparation of the electrode (I) of high work function and high conductivity

A composition (100% by weight) for forming an electrode was prepared comprising highly conductive poly(3,4-ethylenedioxythiophene):poly(sulfostyrene) (PEDOT: PSS) solution (PH500 manufactured by H.C. Starck GmbH, wherein the content of PSS per 1 part by weight of PEDOT is 2.5 parts by weight), polymer 100 solution (by dispersing polymer 100 represented by the following formula in water and alcohol (water: Alcohol = 4.5:5.5 (v/v)) to 5% by weight in a mixture of Aldrich Co.) and 5% by weight dimethyl sulfoxide (DMSO). In this regard, the ratio of the PEDOT:PSS solution and the polymer 100 solution was adjusted so that the content (solid content) of the polymer 100 was 1.0 parts by weight per 1 part by weight of PEDOT. A thin film having a thickness of 100 nm and formed using the composition for forming an electrode had an electrical conductivity of 125 S/cm.

Polymer 100

In polymer 100, x=1300, y=200 and z=1.

The composition for forming an electrode was spin-coated on a polyethylene terephthalate (PET) substrate and heat-treated at 150° C. for 30 minutes to form an electrode 1 having a thickness of 100 nm.

Then, electrodes 2, 3 and 4 were prepared on the PET substrate in the same manner as in the preparation of electrode 1, except that the ratios of PEDOT:PSS solution and polymer 100 solution were adjusted so that the ratio of polymer 100 per 1 part by weight of PEDOT The contents were 2.3 parts by weight, 4.9 parts by weight and 11.2 parts by weight, respectively, wherein the surface of the electrodes 1-4 in contact with the PET substrate was the first surface, and the opposite surface thereof was the second surface.

The conductivities of electrodes 1, 2, 3 and 4 measured using a 4-point probe were 125, 75, 61 and 50 S/cm, respectively.

Comparative example A

Electrode A was prepared in the same manner as in the preparation of Electrode 1, except that a composition comprising a PEDOT:PSS solution and 5 wt% DMSO but not Polymer 100 solution was used.

Evaluation Example 1: Evaluation of Electrode (I)

<Evaluation of molecular concentration with respect to electrode depth>

The molecular concentrations in the surfaces of electrodes 1-4 and A were evaluated by using X-ray photoelectron spectroscopy (XPS, manufactured by VG Scientific, model ESCALAB 200iXL), and the results are shown in Table 1. FIG. 6 shows the XPS spectrum of the electrode 4 with respect to the sputtering time of the electrode 4, ie the depth. The concentration of each fraction was evaluated by analyzing the peaks of PEDOT (164.5 eV), PSS and PSSH (S2p) (168.4 and 168.9 eV) and polymer 100 ( _CF2 , F1s).

Referring to Fig. 6, in the direction from the second surface of electrode 4 (sputtering time = 0 seconds) to the first surface of electrode ₄ , the concentration of CF moiety indicating the concentration of polymer 100 decreases significantly, but the concentration of PEDOT A significant increase. Therefore, the concentrations of PEDOT:PSS and the polymer 100 in the electrode 4 have a concentration gradient according to the depth of the electrode 4 .

In Table 1, the fluorine/PSS ratio calculated from the PSS peak (S2p) and the fluorine peak (F1s) of the second surface of the electrodes 1-4 are listed. Referring to Table 1, as the amount of the polymer 100 increases, the content of the polymer 100 on the surface of the electrodes 1-4, that is, the second surface increases.

Table 1

PEDOT/PSS/Polymer 100 PSS peak surface Fluorine peak area Fluorine/PSS

(weight ratio) product Compare electrode 4 1/2.5/112 220.0718 3571.604 8.764 electrode 3 1/2.5/4.9 508.1833 7793.913 8.282 electrode 2 1/2.5/2.3 412.4424 4589.502 6.001 electrode 1 1/2.5/1.0 696.8955 7118.15 5.516 Electrode A 1/2.5/0 311.484 0 -

<Evaluation of Work Function and Conductivity>

The work functions of the electrodes 1-4 and A were measured in air (manufactured by Niken Keiki, model AC2) using ultraviolet photoelectron spectroscopy, and the results are shown in Table 2.

Table 2

Since the work functions were evaluated for the electrodes 1-4 and A formed on the PET substrate, the work functions shown in Table 2 can be regarded as the work functions of the respective second surfaces of the electrodes 1-4.

<Evaluation of Optical Transmittance>

The optical transmittances of electrodes 1-4 and A were evaluated using a UV spectrometer (SCINCO (S-3100)), and the results are shown in FIG. 7 . For comparison, the optical transmittance of ITO having a thickness of 100 nm is also shown. Referring to FIG. 7, the electrodes 1-4 have excellent optical transmittance, such as excellent visible light transmittance, especially excellent blue visible light transmittance.

<Evaluation of Surface Properties>

The surface roughness of the surfaces of electrodes 1-4 and A, that is, the second surface was evaluated using an atomic force microscope, and the results are shown in Table 3.

table 3

Electrode No. 4 3 2 1 A

Surface roughness (nm) 0.425 0.471 0.367 0.572 0.847

Referring to Table 3, electrodes 1-4 have lower surface roughness than electrode A. The surfaces of electrodes 1-4 are flattened by adding polymer 100 thereto.

<Evaluation of Hole Mobility and Hole Injection Efficiency>

Electrodes 1-4 were evaluated for hole mobility and hole injection efficiency, and the results are shown in FIGS. 8 and 9, respectively. When measuring hole mobility and hole injection efficiency, dark injection space charge limited current (DI SCLC) transients are used. Hole-only devices with electrode (electrode 1, 2, 3 or 4)/NPB layer (about 2.6 μm)/Al structure were fabricated and subjected to DI SCLC transients. While performing DI SCLC transients, a pulse generator (HP214B) and a digital oscilloscope (Agilent Infiniium 54832B) were used. 8 and 9, electrodes 1-4 have excellent hole mobility and hole injection efficiency.

Embodiment 2: the preparation of OLED

Form electrode 1 on PET substrate according to embodiment 1 as anode, then form NPB HTL with 20nm thickness, Bebq ₂ :C545T EML with 30nm thickness (wherein the content of C545T is 1.5% by weight), Bebq ₂ ETL with a thickness of 20 nm, Liq ETL with a thickness of 1 nm, and an Al cathode with a thickness of 130 nm to prepare OLED 1 . OLEDs 2-4 were prepared in the same manner as in the preparation of OLED 1, using electrodes 2-4, respectively, instead of electrode 1.

Comparative example 1

OLED A was prepared in the same manner as in Example 2, except that Electrode A prepared according to Comparative Example A was used instead of Electrode 1 .

Comparative example 2

Use Corning 15Ω/cm ² An ITO glass substrate was substituted for the PET substrate on which the electrode 1 was formed. That is, compared with Example 2, a glass substrate was used instead of the PET substrate, and an ITO electrode was used instead of the electrode 1 . A PEDOT:PSS solution (CLEVIOS ^™ P VP AI4083) in which the content of PSS per 1 wt. part of PEDOT is 6 wt. :PSS HIL. NPB HTL with a thickness of 20 nm, Bebq ₂ :C545TEML with a thickness of 30 nm (wherein the content of C545T is 1.5% by weight), Bebq ₂ ETL with a thickness of 20 nm, Liq ETL with a thickness of 1 nm, and Liq ETL with a thickness of 1 nm were sequentially formed on the HIL by vacuum deposition. 130nm thick Al cathode to prepare OLED B.

Comparative example 3

OLED C was prepared in the same manner as in Comparative Example 2, except that 2TNATA was deposited on the ITO electrode to form 2TNATA HIL with a thickness of 50 nm instead of PEDOT:PSS HIL.

The structure and flexibility of OLEDs 1-4 and A-C are shown in Table 4 below.

Table 4

O: very high (OLEDs are not brittle after bending them 100 times at a radius curvature of 0.75 cm and a strain of 1.25%)

X: Low (OLED is brittle after bending it 100 times at a radius curvature of 0.75 cm and a strain of 1.25%)

Evaluation Example 2: Evaluation of OLEDs

OLEDs 1-4 and A-C were evaluated for efficiency, brightness and lifetime using a Keithley 236 source measure unit and a Minolta CS 2000 spectroradiometer, and the results are shown in Figures 10-12.

Referring to Figures 10-12, it was determined that OLEDs 1-4 had better efficiency, higher brightness and longer lifetime than OLEDs A-C.

Embodiment 3: the preparation of the electrode (II) of high work function and high conductivity

A composition (100% by weight) for forming an electrode was prepared comprising a highly conductive poly(3,4-ethylenedioxythiophene): poly(sulfonylstyrene) (PEDOT :PSS) solution (CLEVIOS ^™ PH500 manufactured by Heraeus GmbH.&Co (formerly HC Starck GmbH), wherein the content of PSS per 1 part by weight of PEDOT is 2.5 parts by weight), 2% by weight of 3 as a fluorinated oligomer ,3,3,-trifluoropropyl)trichlorosilane (CF ₃ CH ₂ CH ₂ SiCl ₃ ) (manufactured by Aldrich Co.) and 5% by weight of dimethyl sulfoxide (DMSO). The composition for forming an electrode was spin-coated on a PET substrate and heat-treated at 150° C. for 30 minutes to form an electrode 5 having a thickness of 100 nm. Electrode 5 has a conductivity of 350 S/cm and a work function of 5.25 eV.

Embodiment 4: the preparation of the electrode (II) of high work function and high conductivity

The composition for forming the electrode 4 of Example 1 was prepared, wherein the ratio of the PEDOT:PSS solution and the polymer 100 solution was adjusted so that the content of the polymer 100 was 11.2 parts by weight per 1 part by weight of PEDOT. Then, 5% by weight of silver nanowires (type ST 164, length: 7.2 μm, diameter: 52 nm, Seashell Technology, LLC) were added to 100% by weight of the composition.

The composition including silver nanowires was spin-coated on a PET substrate and heat-treated at 150° C. for 30 minutes to form an electrode 6 having a thickness of 100 nm. Electrode 6 has a work function of 5.8 eV and a conductivity of 85 S/cm.

As described above, according to one or more of the above embodiments of the present invention, the high work function and high conductivity electrode may be used as an anode of various electronic devices, especially organic light emitting devices and organic solar cells. In this regard, since the high work function and high conductivity electrode has a high work function, there is no need for HIL and/or HTL for controlling work function, or a hole extraction layer together with the EML or photoactive layer. Therefore, electronic devices can be simplified by using the high work function and high conductivity electrodes, and thus their manufacturing costs can be reduced. Also, since the high work function and high conductivity electrode is a polymer-based electrode, it can be effectively applied to flexible electronic devices as well as flat electronic devices.

While the invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that forms may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. and variations in details.

Claims (18)

1. electronic device, including:

High work function and the electrode of high conductivity, described electrode includes the conductive material with the electrical conductivity of 0.1S/cm or bigger And low-surface-energy material, and there is first surface and the second surface contrary with described first surface, wherein at described second table The concentration of low-surface-energy material described in face is more than the concentration of the described low-surface-energy material of described first surface, and described second The work function on surface is 5.0eV or bigger；

The hole transmission layer being placed on the described second surface of described electrode and contact with the described second surface of described electrode；

It is placed in the emission layer on described hole transmission layer or photoactive layer；With

It is placed in the negative electrode on described emission layer or described photoactive layer,

Wherein said low-surface-energy material is the material based on fluorinated silane represented by following formula 10:

Formula 10

X-M^f _n-M^h _m-M^a _r-(G)_p

Wherein

X is end group；

M^fFor being derived from the condensation reaction system of the non-fluorinated monomer by PFPE alcohol, polyisocyanates and isocyanate-reactive The unit of standby fluorinated monomer or the C of fluorination₁-C₂₀Alkylidene；

M^hFor being derived from the unit of non-fluorinated monomer；

M^aFor having by-Si (Y₄)(Y₅)(Y₆) unit of silicyl that represents,

Wherein, Y₄、Y₅And Y₆It is each independently halogen atom, substituted or unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl or the substituent group that can hydrolyze, wherein Y₄、Y₅And Y₆At least one be the substituent group that can hydrolyze,

G is the monovalent organic groups including chain-transferring agent；

N is the number of 1-100；

M is the number of 0-100；

R is the number of 0-100, and r does not include 0；

Wherein n+m+r >=2, and

P is the number of 0-10.

2. the electronic device of claim 1, the concentration of wherein said low-surface-energy material is from described first surface to described It is gradually increased on the direction on two surfaces.

3. the electronic device of claim 1, wherein said conductive material include polythiophene, polyaniline, polypyrrole, polystyrene, Sulfonated polystyrene, poly-(3,4-ethyldioxythiophene), the conducting polymer of auto-dope, its any derivant and arbitrarily Combination.

4. the electronic device of claim 1, the electrode of wherein said high work function and high conductivity farther include following extremely Few one: metal nanometer line, semiconductor nanowires, metallic nanodots, CNT, Graphene, the graphene oxide of reduction, And graphite.

5. the electronic device of claim 4, at least one of which is by-S (Z₁₀₀) or-Si (Z₁₀₁)(Z₁₀₂)(Z₁₀₃) part that represents It is attached to described metal nanometer line, described semiconductor nanowires and the surface of described metallic nanodots, wherein Z₁₀₀、Z₁₀₁、Z₁₀₂With Z₁₀₃It is each independently hydrogen atom, halogen atom, substituted or unsubstituted C₁-C₂₀Alkyl or substituted or unsubstituted C₁- C₂₀Alkoxyl.

6. the electronic device of claim 1, the electrode of wherein said high work function and high conductivity by use include described in lead Prepared by the compositions being used for being formed electrode of electric material, described low-surface-energy material and solvent, wherein said solvent includes being selected from At least one following polar organic solvent: ethylene glycol, glycerol, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

7. the electronic device of claim 1, the work function of wherein said second surface is in the range of 5.0eV-6.5eV.

8. the electronic device of claim 1, wherein said electronic device includes organic luminescent device or organic solar batteries.

9. the electronic device any one of claim 1-8, wherein said emission layer has bigger than the work function of tin indium oxide 0.3eV or more ionization potential.

10. the electronic device any one of claim 1-8, wherein said photoactive layer has bigger than the work function of tin indium oxide 0.3eV or more ionization potential.

The electronic device of 11. claim 1, in formula 10, wherein X is halogen atom, M^fC for fluorination₁-C₁₀Alkylidene, M^hFor C₂-C₁₀Alkylidene, Y₄、Y₅And Y₆It is each independently halogen atom, and p is 0.

The electronic device of 12. claim 1, formula 10 material based on fluorinated silane represented is CF₃CH₂CH₂SiCl₃。

13. electronic devices, including:

High work function and the electrode of high conductivity, described electrode includes the conductive material with the electrical conductivity of 0.1S/cm or bigger And low-surface-energy material, and there is first surface and the second surface contrary with described first surface, wherein at described second table The concentration of low-surface-energy material described in face is more than the concentration of the described low-surface-energy material of described first surface, and described second The work function on surface is 5.0eV or bigger；

The emission layer being placed on the described second surface of described electrode and contact with the described second surface of described electrode or light are lived Property layer；With

It is placed in the negative electrode on described emission layer or described photoactive layer,

Wherein said low-surface-energy material is the material based on fluorinated silane represented by following formula 10:

Formula 10

X-M^f _n-M^h _m-M^a _r-(G)_p

Wherein

X is end group；

M^fFor being derived from the condensation reaction system of the non-fluorinated monomer by PFPE alcohol, polyisocyanates and isocyanate-reactive The unit of standby fluorinated monomer or the C of fluorination₁-C₂₀Alkylidene；

M^hFor being derived from the unit of non-fluorinated monomer；

M^aFor having by-Si (Y₄)(Y₅)(Y₆) unit of silicyl that represents,

Wherein, Y₄、Y₅And Y₆It is each independently halogen atom, substituted or unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl or the substituent group that can hydrolyze, wherein Y₄、Y₅And Y₆At least one be the substituent group that can hydrolyze,

G is the monovalent organic groups including chain-transferring agent；

N is the number of 1-100；

M is the number of 0-100；

R is the number of 0-100, and r does not include 0；

Wherein n+m+r >=2, and

P is the number of 0-10.

The electronic device of 14. claim 13, in formula 10, wherein X is halogen atom, M^fC for fluorination₁-C₁₀Alkylidene, M^h For C₂-C₁₀Alkylidene, Y₄、Y₅And Y₆It is each independently halogen atom, and p is 0.

The electronic device of 15. claim 13, formula 10 material based on fluorinated silane represented is CF₃CH₂CH₂SiCl₃。

16. electronic devices, its use high work function and electrode of high conductivity, described electrode includes having 0.1S/cm or bigger The conductive material of electrical conductivity and low-surface-energy material, and there is first surface and second table contrary with described first surface Face, wherein described in described second surface, the concentration of low-surface-energy material is more than the described low-surface-energy material of described first surface The concentration of material, and the work function of described second surface is 5.0eV or bigger；

Wherein said low-surface-energy material is the material based on fluorinated silane represented by following formula 10:

Formula 10

X-M^f _n-M^h _m-M^a _r-(G)_p

Wherein

X is end group；

M^fFor being derived from the condensation reaction system of the non-fluorinated monomer by PFPE alcohol, polyisocyanates and isocyanate-reactive The unit of standby fluorinated monomer or the C of fluorination₁-C₂₀Alkylidene；

M^hFor being derived from the unit of non-fluorinated monomer；

M^aFor having by-Si (Y₄)(Y₅)(Y₆) unit of silicyl that represents,

Wherein, Y₄、Y₅And Y₆It is each independently halogen atom, substituted or unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀Aryl or the substituent group that can hydrolyze, wherein Y₄、Y₅And Y₆At least one be the substituent group that can hydrolyze,

G is the monovalent organic groups including chain-transferring agent；

N is the number of 1-100；

M is the number of 0-100；

R is the number of 0-100, and r does not include 0；

Wherein n+m+r >=2, and

P is the number of 0-10.

The electronic device of 17. claim 16, in formula 10, wherein X is halogen atom, M^fC for fluorination₁-C₁₀Alkylidene, M^h For C₂-C₁₀Alkylidene, Y₄、Y₅And Y₆It is each independently halogen atom, and p is 0.

The electronic device of 18. claim 16, formula 10 material based on fluorinated silane represented is CF₃CH₂CH₂SiCl₃。